Polyester plastic compositions containing bis-phenoxy flame retardants

ABSTRACT

Plastic compositions containing polyesters and bis-phenoxy compounds having the formula:   WHEREIN Z is bromine, m and M&#39;&#39; are integers having a value of 14, i and i&#39;&#39; are integers having a value of 1 or 2, alkylene is a straight or branched chain alkylene group having from 1 to 6 carbon atoms and A is cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl or halobenzyl.

United States Patent Anderson Jan. 21, 1975 POLYESTER PLASTIC COMPOSITIONS CONTAINING BIS-Pl-IENOXY FLAME RETARDANTS Inventor: Arnold L. Anderson, Alma, Mich.

Michigan Chemical Corp., St. Louis, Mich.

Filed: Feb. 8, 1973 App]. No.: 330,798

Related US. Application Data Continuation-in-part of Ser. No. 260,240, June 6, i972, abandoned.

Assignee:

US. Cl. 260/45.9 R, 260/40 R, 260/45.75 R, 260/45.95 G

Int. Cl C08g 51/60 Field of Search.... 260/45.9 R, 45.95 G, 613 B, 260/33.2 R, 2.5 A], DIG. 24; 106/15 FP References Cited UNITED STATES PATENTS 4/1972 Yanagi et a] l6l/403 3,717,609 2/l973 Hutner 2610/4595 (i Primary Examiner-M. J. Welsh Attorney, Agent, or Firm-Robert E. Hartenhcrgcr;

Robert S. Frieman; James J. Mullen [57] ABSTRACT Plastic compositions containing polyesters and hisphenoxy compounds having the formula:

17 Claims, No Drawings POLYESTER PLASTIC COMPOSITIONS CONTAINING BIS-PI-IENOXY FLAME RETARDANTS This application is a continuation-in-part of copend- 5 ing application Ser. No. 260,240, filed June 6, 1972 and now abandoned. The entire specification of this case, Ser. No. 260,240, is to be considered as incorporated herein by reference.

The prior art considered in conjunction with the preparation of this application is as follows: US. Pat. Nos. 2,130,990; 2,186,367; 2,329,033; 3,666,692; 3,686,320; 3,658,634; German Pat. No. 1,139,636; German Pat. No. 2,054,522; Japanese Pat. No. (72) 14,500 as cited in Volume 77, Chemical Abstracts, column l53737k (1972); Chemical Abstracts, Volume 13, column 448 Chemical Abstracts, Volume 31, column 7045 and Journal of the Chemical Society, pages 29722976 (1963). All of these publications are to be considered as incorporated herein by reference.

The present invention relates to plastic compositions containing saturated or unsaturated polyesters (both types herein referred to collectively as polyesters). More specifically, the present invention covers plastic compositions containing polyesters and certain bisphenoxy compounds (hereinafter defined) as flame retardants for said plastic compositions.

Polyester plastics (also commonly called resins) and utility thereof are known in the art as exemplified by Polyesters and Their Applications, Bjorksten Research Laboratories, Inc., Reinhold Publishing Corporation, New York, 1956 and Modern Plastics Encyclopedia 1972-1973, Vol. 49; No. 10A, October, 1972, pages 73, 76, 78, 79 and 156-158 and which publications are in toto incorporated herein by reference.

The need for flame retarding polyesters has also been recognized in the art as exemplified by US. Pat. No. 3,347,822 and US. Pat. No. 3,422,048, and Modern Plastics Encyclopedia,ibid, pages 217, 224-229, 235 and 45 6-458 and which publications are in toto incorporated herein by reference.

The resultant disadvantages in the utilization of various prior art materials as flame retardants for polyesters include, without limitation, factors such as thermal migration, heat instability, light instability, nonbiodegradable, toxicity, discoloration and the large amounts employed in order to be effective. Thus, there is always a demand for a material which will function as a flame retardant in polyesters and concurrently will not, by incorporation therein, adversely effect the chemical and/or physical and/or mechanical properties of the resultant polyester plastic composition.

The prior art problem of providing a flame retarded polyester composition having desired chemical, physical and mechanical properties has now been substantially solved by the present invention and the abovedescribed disadvantages substantially overcome.

Accordingly, one of the main objects of the present invention is to provide polyester plastic compositions which are flame retarded.

Another object of the present invention is to provide a material for polyester plastic compositions which will not substantially adversely effect the chemical and/or physical and/or mechanical properties of said compositions.

A further object of the present invention is to provide a flame retardant which is economic and easy to incorporate into polyester plastics without being degraded or decomposed as a result of blending or processing operations.

[t has been found that the foregoing objects can be obtained by the incorporation of a new class of his phenoxy compounds in polyesters to subsequently provide flame retarded compositions which exhibit outstanding chemical, physical and mechanical properties.

The bis-phenoxy compounds used in the present invention compositions have the formula:

In Formula I above, Z is bromine; m and m are integers each independently having a value of l-4; i and i are integers each independently having a value of'l or 2; alkylene is a straight or branched chain alkylene group having from 1 to 6 carbon atoms (e.g., CH C H C l-I C H C H C H, and CH CH(CH;,)CH and A is from the group cyano (CH), nitro (NO lower alkoxy (e.g., OCH OC H lower alkyl (e.g. CH C H C H C,H fluorine, dialkylamino e.g., N(CH -N(C H phenyl (-C ,H halo-phenyl, benzyl (-CH C H and halo-benzyl.

In Formula I, i or i is 1 when m or m is 4, respectively.

It is to be understood that all of the compounds falling within the above Formula 1 and heretofore defined are generically described herein as bis-phenoxy compounds.

Illustrative (but without limitation) of some of the present invention bis-phenoxy compounds are shown below:

0 (alkylene 0 the exemplary definitions of A, Z, i, i, m, m and alkyl- The above reaction is conducted at temperatures ene are listed in Table I. ranging from the freezmg pomt of the initial reaction Table I Compound No Z m m A I 1' Alkylene 1 Br 2 2 CN 1 1 CH 2 Br 2 2 F 1 1 c 11,, 3 Br 2 2 CN 1 I C H, 4 Br 2 2 -CN 1 1 H, 5 Br 2 2 N0, 1 1 C 11, 6 Br 2 2 -0CH, 1 1 C H, 7 Br 3 3 -0CH, 1 1 C1H4 8 Br 2 2 -CH, 1 1 Cm, 9 Br 2 2 1 I 0,11 10 Br 2 2 -N CH,.) 1 1 c H, 1| Br 2 2 H 1 1 Cm, 12 Br 2 2 C H Br 1 1 C H, 13 Br 2 2 C H 1 1 cm, 14 Br 2 2 CH,C,,H,Br 1 1 0 H, 15 Br 3 3 -C.,H,.C1 1 1 C H l6 Br 3 3 1 1 13,,H, 17 Br 2 2 CN 2 2 C 11, 18 Br 4 4 CN 1 1 cm, 19 Br 3 3 -C,,H,Br 1 1 C 11, 20 Br 3 3 N0 2 2 C 11 21 Br 2 2 -CN 1 1 CH(CH3)CH2 22 Br 4 4 N0, 1 1 cmcrmcmcn, 23 Br 3 3 2 2 CH,CH(CH,)cH,C1-1 24 Br 1 1 -C,H, 1 1 c 1 1 1 oC.H. 1 1 CZH,

In general, the bis-phenoxy compounds are prepared mass to the boiling point thereof. Preferably the temby reacting a halogenated phenol with a halogenated peratures are from about 40 C to about 200 C and alkane at elevated temperatures in the presence of a more preferably from about 50 C to about 175 C. It

basic material such as alkali metal hydroxides, carbonis to be understood that the reaction can be conducted ates, bicarbonates, oxides and hydrides. The preferred under sub-atmospheric (e.g., 1/10-8/10 atmospheres), alkali metals are potassium and sodium. Where one deatmospheric or super-atmospheric (e.g., l.5-l0 atmosires to increase, for example, ease of handling the respheres) pressure. Preferably, the reaction is carried action mass, solvents such as ketones (e.g., acetone, out at atmospheric pressure. methyl ethyl ketone and methyl lsqbutyl ketone) The above-described processes can be carried out cohols (e.g., methanol, ethanol, lso-propyl alcohol, h I d bl h I butyl alcohol and glycols), or aqueous solvents (e.g., Iona tea y aval a e c proqe 5 mg equipment. For example, a conventional glass-lined water a mixture of water and alcohol and a mixture of vessel provided with heat transfer means, a reflux conwater d ketone). can be employed The deslred end denser and a mechanical stirrer can be advantageously product the blsfphenoxy p l can be recov' utilized in practicing any of the preferred embodiments ered from the reaction mass via various methods such of the invention described in the exam [es Set forth as distillation or crystallization. Where the end product herein p requires recovery via crystallization, various aromatic solvents such as benzene, toluene, xylene, dichloroben- The amount of bis-phenoxy compound employed in zene and the like can be used. the present invention compositions is any quantity Specifically, the bis-phenoxy compounds are prewhich will effectively render the polyester containing pared according to the following reactions: composition flame retardant. In general, the amount 2- Z O OH X(alkylene)X 7 2HX A1 A l Z .O (alkylene) O Z u In the above reaction, X is halogen, preferably chloused is from about 1 percent to 25 percent by weight, rine and alkylene is the same as herein defined. Where based on the total weight of the composition. Preferam and m and iand i are different integers, then equivbly, the amount employed is from about 5 percent to alent molar portions of the particular halogenated pheabout 20 percent by weight. It is to be understood that nol are used with equivalent portions of dissimilar haloany amount can be used as long as it does not substangenated phenol. tially adversely effect the chemical and/or physical and/or mechanical properties of the end polymer composition. The amount utilized, however, is such amount which achieves the objectives described herein.

It is to be understood that the term polyesters as used herein means polycondensate products of the reaction of dibasic acids and/or anhydrides or derivatives therefrom with dihydroxy alcohols. This term includes both saturated and unsaturated polyesters but excludes those linear polyesters used for fibers. Unsaturated polyesters are so designated where part or all of the respective acids, anhydrides and/or alcohols contain crosslinkable ethylenic bonds.

Examples of dibasic acids and anhydrides include, without limitation, phthalic anhydride, maleic anhydride, fumaric acid, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, l,4,5,6,7,7-hexachlorobicyclo (2,2,1 )-5- heptene-2,3-dicarboxylic acid i.e. chlorendic acid, isophthalic acid and terephthalic acid.

Examples of dihydroxy alcohols include, without limitation, ethylene glycol, diethylene glycol, propylene glycol, butane glycol, butene diol, hexane diol, hexene diol, butyne diol, cyclohexane diol, cyclohexene diol, neopentyl glycol, hydrogenated bisphenol A, 2,2,4- trimethyl-l ,3-pentanediol and 1,4- cyclohexanedimethanol.

This term also includes copolymers of polyesters which are resins derived from reactants used to give polyester resins and reactants used to give other polycondensate linkages. For example, there may be mentioned the reaction of dibasic anhydrides with dihydroxy alcohols and diamines to give polyester and polyamide links along the same molecular backbone. Also, those products formed by addition polymerization of reactants with ethylenic linkages before or after the polyester condensation reaction. For example, the addition reaction of styrene with unsaturation in polyesters after polycondensation or the formation of an additional polymer with carboxylic acid or other condensable end-groups for further polymerization by polyesterification.

Thus the polyesters used in the present invention compositions is any polyester herein defined and which one so desires to flame retard. It is to be understood that the polyesters used can be a virgin material, i.e., substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like, or the polyesters can have additives (such as those mentioned and described herein) already contained therein or added concurrently with or after the addition of the hisphenoxy compounds.

Another facet of the present invention relates to the use of certain metal compounds with the bis-phenoxy compounds to promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately. These enhancing agents are from the group antimony, arsenic, bismuth, tin and zinc-containing compounds. Without limitation, examples of said enhancing agents include Sb O SbCl SbBr Sbl SbOCl, AS203, AS205, ZIIBO4, BaB O4-H2O, 2.211038 35- H O and stannous oxide hydrate. The preferred enhancing agent is antimony trioxide.

The amount of enhancing agent employed in the present invention compositions is any amount which when used with said bis-phenoxy compounds will promote a cooperative effect therebetween. In general, the amount employed is from about 1 percent to about l5 percent, preferably from about 2 percent to about l0 percent by weight, based on the total weight of plastic composition. Higher amounts can be used as long as the desired end result is achieved.

It is also within the scope of the present invention to employ other materials in the present invention compositions where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promotors; antioxidants; antistatic agents; antimicrobials; colorants, flame retardants such as those listed on pages 456-458, Modern Plastics Encyclopedia, ibid, (in addition to the new class of flame retardants described herein); heat stabilizers; light stabilizers; pigments; plasticizers; preservatives; ultraviolet stabilizers and fillers.

In this latter category, i.e. fillers, there can be mentioned without limitation, materials such as glass; carbon; cellulosic fillers (wood flour, cork and shell flour); calcium carbonate (chalk, limestone, and precipitated calcium carbonate); metal flakes; metallic oxides (aluminum, beryllium oxide and magnesia); metallic powders (aluminum, bronze, lead, stainless steel and zinc); polymers (comminuted polymers and elastomer-plastic blends); silica products (diatomaceous earth, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica); silicates (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate); and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulfide and silicon carbide.

The above mentioned materials, including fillers, are more fully described in Modern Plastics Encyclopedia, ibid, and which publication is incorporated herein (in toto) by reference.

The amount of the above described materials employed in the present invention compositions can be any quantity which will not substantially adversely effect the desired results derived from the present invention compositions. Thus, the amount used can be zero (0) percent, based on the total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about 0 percent to about percent and specifically from about 1 percent to about 50 percent.

The bis-phenoxy compounds can be incorporated in to the polyesters at any processing stage in order to prepare the present invention compositions. In general, this is undertaken prior to fabrication either by physical blending or during the process of forming polyesters per se. Where one so desires, the bis-phenoxy compounds may be micronized into finely divided particles prior to incorporation into the polyesters.

EXAMPLE I A linear saturated polyester plastic material, (Varlox 310, a product of General Electric Company) is utilized as the base resin in order to prepare 26 formulations (plastic compositions) designated Nos. 1-26 in Table II. With the exception of formulation No. l (the control), the particular bis-phenoxy (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic by adding both to a Brabender mixer (Plastic-Corder, Torque Rheometer, Model PLV-l50, C. W. Brabender Instruments Inc., South Hackensack, N. J.). The mixer is equipped with a pair of roller type blades positioned within a head provided with heat transfer means.

The resultant mixture is heated to about 277 C.; at this temperature, it is in a molten state. The percentages by weight of each component utilized in the respective formulations are listed in Table 11. Each formulation is discharged from the mixer and upon cooling solidifies and is ground into chips. The chips are subjected to compression molding in a Wabash press by placing said chips between two platens, the bottom of which contains four equal size depressions 3 inches by 5 inches by Vs inch deep. The top platen is then placed over the bottom platen and heat transfer means supplied thereto in order to melt said chips and thus provide solid samples (after cooling) for testing.

An unsaturated polyester plastic material, Koppers 6101-25, a liquid product of Koppers Company, is used as a base resin In order to prepare 26 formulations, designated Nos. 27-52 in Table II. The particular bisphenoxy (and antimony trioxide where indicated) is incorporated into the unsaturated polyester by mixing with 0.1 percent by weight, based on the total weight of the formulation, cobalt octoate and 2.0% methyl ethyl ketone peroxide to form a liquid mixture. This mixture is poured into said depressions and cured at 100 C under slight compression by the Wabash press. Formulation No. 27, without additives, is the control.

Portions of the solid samples of each respective formulation (Nos. 1-52) prepared according to the above described procedures are then subjected to two different standard flammability tests, i.e., UL 94 and ASTM D-2863-70. The UL 94 is, in general, the application of a burner to a test specimen (strip) for a certain period of time and observation of combustion, burning, and extinguishment. This procedure is fully set forth in Underwriters' Laboratories bulletin entitled UL 94, Standard for Safety, First Edition, September 1972 and which is incorporated herein by reference. ASTM No. D-2863-70 is a flammability test which correlates the flammability of a plastic specimen to the available oxygen in its immediate environment; this correlation is stated as an Oxygen Index, 0.1., level predicated upon the percent oxygen in the gaseous medium which is required to just provide a steady state of continuous burning of the plastic specimen. This ASTM method is fully described in 1971 Annual Book of ASTM Standards Part 27, published by the American Society For Testing and Materials, 1916 Race Street, Philadelphia, Pa.; this publication is to be considered as incorporated (in toto) herein by reference.

The results of these flammability tests are shown in Table 11.

TABLE II FLAMMABILITY DATA FOR POLYESTER PLASTIC COMPOSITIONS CONTAINING BIS-PHENOXY COMPOUNDS FORMULA- BIS-PHENOXY COM- ENHANCING OXYGEN INDEX U1. 94

TION POUND AGENT NO. NO. Sb O "/1 2 1. 0 0 22.0 SB 2. 1 20 0 235 SB 3. l 20 10 27.5 Sl-I-Z 4. 2 20 0 23.0 SB 5. 2 20 10 28.0 511-2 6. 5 20 0 23.5 SB 7. 5 20 10 31.1) 81-1-2 8. 7 20 0 24.0 SB 9. 7 20 10 31.0 Sl-1-I l0. 8 20 0 22.5 SB 11. 8 20 10 28.0 S1-1-2 I2. 10 20 0 23.0 SB 13. 10 20 10 285 51-1-2 14. 12 20 0 230 SB 15. 12 20 10 31.5 Sl-1-2 16. 14 20 0 23.0 SB 17. 14 20 10 31.0 SI-1-2 l8. 16 20 0 23.5 SB 19. 16 20 10 30.5 S1-1-2 20. 18 20 0 24.5 SB 21. 18 20 10 32.0 SI-I-l 22. 21 20 0 23.5 SB 23. 21 20 10 29.0 81-1-2 24. 22 20 0 25.0 SB 25. 22 20 10 33.0 SIB-0 26. 23 2O 10 32.0 SIi-I 27. 0 0 18.0 SB 28. l 20 0 21.0 SB 29. 1 20 10 28.0 312-] 30. 2 20 0 220 SB 31. 2 20 10 28.0 SI-l-l 32. 5 20 0 23.5 SB 33. 5 20 10 30.0 SIi-0 34. 7 20 0 24.0 SB 35. 7 20 10 32.5 315-0 36. 8 20 0 21.5 SB 37. 8 20 10 28.5 Sl-1-1 38. 10 20 0 22.5 SB 39. 10 20 10 28.0 SI-I-l 40. 12 20 0 22.5 SB 41. 12 20 10 30.5 S1-1-0 42. I4 20 0 23.5 SB 43. 14 20 10 31.0 51-1-0 44. 16 2O 0 23.0 SB

45. 16 20 10 30.5 515-0 46. 18 20 0 24.5 SB 47. I8 20 10 32.0 Sl-I-O 48. 21 20 0 22.5 SB 49. 21 20 10 29.0 SB] 50. 22 20 0 24.0 SB 51. 22 20 10 32.5 515-0 52. 23 20 10 31.5 SE-l) Referring to Table II, the bis-phenoxy compound number relates to the structural formulae heretofor set forth in Table I; a difference of 2 percent in the Oxygen Index values is considered significant; and the UL 94 values are on a graduated scale wherein the highest degree to lowest degree of flame retardancy is respectively SE-O, SE-l, SE-Z, SB and Burns.

The results shown in Table II demonstrate the unique effectiveness of these bis-phenoxys as flame retardants for polyesters. With reference to the saturated polyester based formulations (Nos. l26), formulation No. l (the control) had a 0.1. of 22.0 and UL 94 value of SB. The even numbered formulations, employing the use of the particular bis-phenoxy compound all show an increase in fire retardancy as measured by 0.1. While some formulations have a SB rating (UL 94), the individual U.L. rating covers a wide range and consequently, in these cases, the 0.]. numbers are more indicative of increased flame retardancy. The use of an enhancing agent such as Sb O to promote a cooperative effect between such agent and the bis-phenoxy compound is fully demonstrated via the results obtained from testing the odd numbered formulations. The highest UL 94 ratings and significantly higher 01. values are obtained when using an enhancing agent.

The results obtained using an unsaturated polyester, are basically similar to those obtained using the saturated polyester. Formulation Nos. 28-52 all demonstrated a significant increase in 01. values as compared to the control, No. 27.

EXAMPLE II Portions of the solid samples of Formulation Nos. 1-52 prepared according to the above described procedure of Example I are subjected to the following ASTM tests in order to ascertain other properties of the resultant plastic composition:

(1) Tensile Strength Temperature (HDT) ASTM Test No. D648-56.

Each of the aforementioned ASTM Tests are standard tests in the art and are utilized collectively in order to ascertain the efficacy of a polymeric system as an overall flame retarded composition for commercial application. (Formulation Nos. 27-52 are not sub jected to the Izod Impact test since they are not reinforced and consequently, impact testing is not approp'riate since any data obtained would not have significant meaning). All of these ASTM Tests are to be considered as incorporated herein by reference.

The results of these ASTM tests show that the physical properties of the present invention compositions are basically the same (except 0.1. and UL 94 values) as the plastic material without the flame retardant (i.e., formulation Nos. 1 and 27). Thus, there is no substantial adverse effect on the physical properties of the plastic material when the novel compounds are incorporated therein.

EXAMPLE Ill The procedure of Examples I and II are repeated except that the enhancing agent used is zinc borate instead of Sb O Substantially the same results are obtained using zinc borate as those obtained using Sb O EXAMPLE IV Strip samples of each of Formulation Nos. 1 through 52 Table II, are subjected to light stability tests via the use ofa Weather-Ometer, model 25/18 W. R., Atlas Electrical Devices Company, Chicago, Illinois. Utilizing an operating temperature of F and a 50 percent relative humidity, each strip is subjected to 200 hours of simulated daylight via the use of a carbon arc. The results show that after 200 hours, there is no significant discoloration in any strip tested and which demonstrates that the present invention compositions are highly resistant to deterioration by light.

EXAMPLE V Samples of each of Formulation Nos. 1 through 52 Table II, are subjected to temperature (thermal) stability tests via the use of thermal gravimetric analysis (TGA). This test employed the use of a Thermal Balance, model TGS-l, Perkin-Elmer Corporation, Norwalk, Connecticut and an electrical balance, Cahn 2580 model, Cahn Instrument Company, Paramount, Calif. The results of these tests show that the hisphenoxy compound containing Formulations had more than adequate stability for melt processing and subsequent heat aging (i.e. high temperature applications) and thus demonstrating that the particular bis-phenoxy are quite compatible with the plastic material. The bisphenoxy compound stability thus aids in providing sufficient flame retardancy at the plastic decomposition temperature. This test also demonstrates that these compounds do not exhibit migration.

In view of the foregoing Examples and remarks, it is seen that the plastic compositions, which incorporate these compounds, possess characteristics which have been unobtainable in the prior art. Thus, the use of these compounds in the above described plastic material as flame retardants therefor is quite unique since it is not possible to predict the effectiveness and functionality of any particular material in any polymer system until it is actively undergone incorporation therein and the resultant plastic composition tested according to various ASTM Standards. Furthermore, it is necessary, in order to have commercial utility, that the resultant flame retarded plastic composition possess characteristics such as being non-toxic. Use of these compounds in the plastic material has accomplished all of these objectives.

The above examples have been described in the foregoing specification for the purpose of illustration and not limitation. Many other modifications and ramifications will naturally suggest themselves to those skilled in the art based on this disclosure. These are intended to be comprehended as within the scope of this invention.

What is claimed is:

l. A plastic composition containing polyesters having incorporated therein an effective amount of a flame retardant which is a bis-phenoxy compound having the formula:

(alkylene) 0 wherein Z is bromine; m and m are integers having a value of l-4; i and i are integers having a value of 1 or 2; alkylene is a straight or branched chain alkylene group having from 1 to 6 carbon atoms; and A is selected from the group consisting of cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl, or halobenzyl, with the proviso that when m or m is 4, i or i respectively is 1.

2. The composition as set forth in claim 1 wherein i and i are both 1.

3. The composition as set forth in claim 1 wherein i and i are both 2.

4. The composition as set forth in claim 2 wherein A is cyano.

5. The composition as set forth in claim 2 wherein A is nitro.

6. The composition as set forth in claim 2 wherein A is lower alkoxy.

7. The composition as set forth in claim 2 wherein A is lower alkyl.

8. The composition as set forth in claim 2 wherein A is fluorine.

9. The composition as set forth in claim 2 wherein A is dialkylamino.

10. The composition as set forth in claim 2 wherein A is phenyl.

11. The composition as set forth in claim 2 wherein A is halo-phenyl.

12. The composition as set forth in claim 2 wherein A is benzyl.

13. The composition as set forth in claim 2 wherein A is halo-benzyl.

14. The composition as set forth in claim 1 wherein alkylene is CH 15. The composition as set forth in claim 1 wherein alkylene is C H 16. The composition as set forth in claim I wherein alkylene is C H 17. The composition as set forth in claim I wherein alkylene is C l-l 

2. The composition as set forth in claim 1 wherein i and i'' are both
 1. 3. The composition as set forth in claim 1 wherein i and i'' are both
 2. 4. The composition as set forth in claim 2 wherein A is cyano.
 5. The composition as set forth in claim 2 wherein A is nitro.
 6. The composition as set forth in claim 2 wherein A is lower alkoxy.
 7. The composition as set forth in claim 2 wherein A is lower alkyl.
 8. The composition as set forth in claim 2 wherein A is fluorine.
 9. The composition as set forth in claim 2 wherein A is dialkylamino.
 10. The composition as set forth in claim 2 wherein A is phenyl.
 11. The composition as set forth in claim 2 wherein A is halo-phenyl.
 12. The composition as set forth in claim 2 wherein A is benzyl.
 13. The composition as set forth in claim 2 wherein A is halo-benzyl.
 14. The composition as set forth in claim 1 wherein alkylene is CH2.
 15. The composition as set forth in claim 1 wherein alkylene is C2H4.
 16. The composition as set forth in claim 1 wherein alkylene is C3H6.
 17. The composition as set forth in claim 1 wherein alkylene is C4H8. 